Coloring of products comprising cellulose acetate



Patented Dec. 24, 1929 UNITED STATES PATENT OFFICE GEORGE HOLLAND ELLIS OF SPONDON, NEAR DERBY, ENGLAND, ASSIGNOR TO CELA- NESE CORPORATION OF AMERICA, A CORPORATION OF DELAWARE COLORING- OF PRODUCTS COMPRISING CELLULOSE ACETATE No Drawing. Original application filed September 25, 1923, Serial No. 664,780, and in Great Britain January 27, 1923. Divided and this application filed December 27, 1928. Serial No. 157,409.

This invention relates to the dyeing which term includes printing and stencilling of artificial yarns or threads, filaments, fabrics, films or other products made of or contain- 3 ing cellulose acetate.

i According to the invention of U. S. ap-

plication S. N 0. 664,780, coloring matters or organic compounds which have an afiinity for cellulose acetate or are capable of color- 19 ing the same but which are insoluble or practically insoluble in water or are of relatively low solubility in water, all of which are hereinafter included in the expression relatively water-insoluble compounds, are applied for is the dyeing or coloring of threads, filaments,

fabrics, films or other products such as referred to, by employing them in the form of solubilized i. e. soluble or more soluble m'odifications, obtained by pretreating them with bodies having oily or fatty characteristics, containing salt-forming groups capable of forming soluble salts with alkalies or ammonia, for example the sulpho group or the carboxyl group or both sulpho and carbonyl groups, or salts of such bodies such for instance as their sodium or other alkali salts or ammonium salts. Such bodies and their salts are hereinafter, as in the said application, included in the term body of oily or fatty characteristics, In particular one can employ sulphoricinoleic acid or other sulphonated fatty acids or salts thereof such as referred to, but other bodies of oily or fatty characteristics may be employed, such as oleic, stearic or palmitic acid, or salts thereof such for instance as the sodium or other alkali salts or ammonium salts. Mixtures of 7 two or more than two of any of the aforesaid solubilizing agents may be employed.

The invention may especially be employed for dyeing cellulose acetate with non-sub phonated or other insoluble or relatively insoluble organic compounds or coloring matters of the azo class. it may likewise be employed for dyeing cellulose acetate by the azoic or development process with simple amino bases other than amino azo coloring matters, or by any other coloring matters or compounds having an aiiinity for or capable of coloring cellulose acetate, but the use of which by the ordinary methods is impracticable or diflicult owing to their insolubility or low solubility in water, such for example as unreduced coloring matters, of the substituted quinone mono-imide class, generally comprised within the term indophenols; or coloring matters or compounds of the follow- 1ng classes usually containing no sulpho groups diphenylmethane, triphenylmethane, triarylmethane, oxazine, azine, diazine, thiazine, unreduced indigoid, or basic derivatives of the anthraquinone series; as instances may be mentioned, rosaniline base, alkylated or arylated rosaniline bases, pararosaniline base, tetramcthyl-diparaamidotriphenyl carbinol (malachite green base), amino anthraquinones and aminohydroxy-anthraquinones or their derivatives, such as l hydroxy 4e: paratoyl amino anthraquinone, 1: paratolyl amino i methyl-amino-anthraquinone, safranine base, and so forth.

The present application is a divisional application from the said U. S. application S. No. 664,780 and has for object to claim specifically the employment in the aforesaid processes of unreduced coloring matters of the substituted quinone monoimide class generally comprised Within the term indophenols.

It is known that the aflinities of acetyl cellulose for various coloring matters are large 1y influenced by the chemical groups comprised in the constitutions of the molecules of the coloring matters, the groups; azo, amino, imino, imide, nitro, nitroso, isonitroso, hydroXyl, acidylaniino being favourable. For example, it may be stated that the group NH and its alkyl substituents, and the group NN-- are very favourable, the groups NO and -1OH are somewhat favourable, but the group SO H is very unfavourable to the fixation of the coloring matter by the acetyl cellulose material.

In carrying out the invention, the organic compounds or coloring matters having an afiinity for or capable of dyeing acetyl collulosemay be dissolved in the body or bodies of oily or fatty characteristics and be afterwards added to the dye baths. Some of the coloring matters or compounds for instance dissolve easily direct in the alkali or ammocan be conducted in the usual manner.

It is of course understood that'mixtures of different coloring matters or organic compounds of the character hereinbefore referred to may be applied in theform of modifications solubilized or rendered more soluble by the solubilizing bodies of oily or fatty characteristic-s. Also that mixtures of such solubilizing bodies may be employed for solubilizing any of the compounds or.

coloring matters to beapplied according to the invention.

Other coloring matters which are not deleteriously affected by the sulphonated fatty acid or salt or other body of oily or fatty characteristics may, when desired, be dyed on to the material together with the coloring matters or compounds of the character be fore indicated. A

The compounds or coloring matters to be applied according to the invention may if desired be made into solid solutions or complexes or other concentrated preparations suitable for transport and subsequent dissolving and application, by heating them with the body or bodies of oily or fatty characteristics such as referred tofor example oleic, stearic, palmitic or sulphoricinoleic acid etc. or their salts either by treatment in presence of little or no water, or by treatment in presence of larger quantities of-water with subsequent concentration or drying. For example the preparations may be made by heating the organic compound or compounds or coloring matter or coloring matters with the body or bodies of oily or fatty characteristics and neutralizing or mixing while hot,

; with alkalies or ammonia as such, or in saturated or nearly saturated solutions. Or the coloring matters or compounds may be dissolved direct in the hot alkali salt or ammonium salt of,the fatty or oily body or soap to give a solid solution or complex or concentrated preparation on cooling, and, where necessary drying.- To gdye the acetyl cellulose material the solid solution or complex made as above maybe simply dissolvedin hot water, the resultant solution being added to. water in a suitable vessel and the dyeing be conducted as usual.

It is understood that the invention also extends to the dyeing of mixed fabrics or materials containing cellulose acetate asso-' ciated with cotton,'silk, wool or other threads or fibres with the classes of organic comtra e e0 solubilized modifications, in the dye bath and dyeing be proceeded with in the usual manner. Where the several dyestuffs or compounds and the requisite assistants are compatible and will mix together without deleterious efiect the suitable coloring matter or coloring matters for the other fibre or fibres may be added to the same bath. Where this is not possible, these other fibers may be first selectively dyed by the application of suitable dyestuffs, and the acetyl cellulose be afterwards dyed selectively as above, or vice versa.

Instead of dyeing the mixed goods in uniform shades or in contrasting colors, the cellulose acetate portion may be dyed, leaving undyed the other fibre or one or more other fibres associatel therewith. V

This invention is likewise applicable to the printing or stencilling of threads, fabrics or materials consisting of acetyl cellulose alone or associated with other fibres or materials. For this purpose, in applying the compound or coloring matters having an affinity for acetyl cellulose, suitable amounts of their modifications obtained by treating them with sulphonated fatty acids or other bodies of oily or fatty characteristics, as above referred to, may be dissolved in water, thickened with substances such as starch, gums, dextrin, flour and the like, and the pastes thus formed be applied to the material consisting of or containing' acetyl cellulose by printing from rollers, blocks, etc., or by stencilling, the material being then dried The drying is often sufficient to fix the coloring matter, compound or primary amido base well enough, in other cases the material may be subjected to a short treatment with steain or aging. The

'printe'dor stencilled material may be washed or not as desired,and be finished as may be necessary.

Mixtures of different organ c compounds or coloring matters may of course be applied.

.of the substituted quinone monoimide class,

it has been found that these are very-useful for acetyl cellulose, many of the members of the class having very good direct aflinity or dyeing properties for it and yielding shades, e. g. blues and violets, which are not easily attainable with simple azo coloring matters. The results, moreover, are often very resistant to light and soaping.

Generally it willbe understood that in dyeing, printing or sten'cilling ofmaterials consisting of or containing cellulose acetate, with the solubilized modifications of any of'the 3 kilos of diethyl para amino phenyl 1:4

naphthoquinone monoimide (33% paste) (Ci I s)2.

A a o are well mixed with 15 litres of 50% sodium salt of sulphoricinoleic acid which has previously been heated to 100 C. After about 10 minutes the mass is diluted with boiling water andthe whole is filtered into the dye machine containing cold, soft water. Volume of dye bath about 30 1 on theweight of the fabric. The fabric is entered and'worked as usual, the temperature being raised and dyeing continued until the desired depth of shade is-produced. The fabric is then removed,

' rinsed, and dried and finished as desired.

i lVhat I claim and desire to secure by Letters Patent is 1. In and for the dyeing of yarns, fabrics 'and other' products comprising cellulose acetate, the employment of relatively waterinsoluble unreduced indophenol coloring matters, said coloring matters being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a body of oily or fatty characteristics.

- 2. In and for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterinsoluble unreduced indophenol coloring matters. saidv coloring matters being employed in the form of solubilized modifications ob tained by pretreating them with a solubilizing agent comprising-a higher fatty acid compound.

3. In and for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterinsoluble unreduced indophenol coloring matters, said coloring matters being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a sulphonated higher fatty acid compound.

4. In and for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterinsoluble unreduced indophenol coloring matters, said coloring matters being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a salt of a higher fatty acid.

5. In and for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterinsoluble unreduced indophenol coloring matters, said coloring matters being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a salt of a sulphonated higher fatty acid.

6. In and for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterinsoluble unreduced indophenol coloring matters, said coloring matters being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a sulphonated ricinoleic acid compound. I

7. In and for the dyeing of yarns, fabrics and other products comprising cellulose 1 acetate, the employment of relatively watermatters, said coloring matters being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising a salt of sulphori'cinoleic acid.

8. In and for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterins'oluble unreduced indophenol coloring matters, said coloring matters being employed in the form of solubilized modifications obtained by pretreating them with a solubilizing agent comprising sodium salt of sulphoric-inoleic acid.

In testimony whereof I have hereunto subscribed my name.

GEORGE HOLLAND ELLIS.

insoluble unreduced indophenol coloring 

